Process for producing coextruded film of polypropylene, polypropylene blend, and nylon

ABSTRACT

A novel coextruded plastic film has as an adhesive layer between polypropylene and nylon layers, a blend of polypropylene and a graft copolymer of maleic anhydride onto a polypropylene backbone, the graft copolymer having been produced in a reaction carried out at a temperature of from about 80° C. up to about 10° C. below the melting point of the polypropylene.

This is a division of application Ser. No. 236,601, filed Feb. 20, 1981,now U.S. Pat. No. 4,361,628, issued Nov. 30, 1982.

BACKGROUND OF THE INVENTION

This invention pertains to coextruded plastic films, and particularly,to those films having a polypropylene layer adhered to a layer of anylon-type polyamide. In such films, the adhesion between the nylon andpolypropylene layers has been particularly troublesome. It has beensurprisingly found that an excellent adhesive for the coextrusion ofnylon and polypropylene is a blend of a graft copolymer of maleicanhydride onto a polypropylene backbone and an ungrafted polypropylene,the graft copolymer having been produced in a reaction carried out at atemperature of from about 80° Celsius up to about 10° Celsius below themelting point of the polypropylene, the graft copolymer containing fromabout 0.10% to about 2.5% maleic anhydride based on the total weight ofthe graft copolymer, the graft copolymer comprising between about 5% andabout 30% by weight of the blend.

The graft copolymer reaction preferably took place in the presence of anorganic peroxide. The polypropylene layer may contain up to about 4%polymeric ethylene.

In the coextrusion of a 5-layer film, the structure includes a fourthlayer, of ethylene vinyl alcohol copolymer (EVOH), affixed on one of itssurfaces to the nylon, and a fifth layer, of nylon, affixed to the othersurface of the EVOH.

Thus the process comprises coextruding polypropylene, and nylon with theadhesive blend juxtaposed therebetween. In the formation of a five layerstructure containing EVOH, the process comprises coextruding the fivelayer structure of, in sequential order in the structural layering, fromone outside surface to the other: polypropylene, adhesive blend, nylon,EVOH, and nylon.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-section of a three layer coextruded structure of thisinvention.

FIG. 2 is a cross-section of a five layer coextruded structure of thisinvention.

DETAILED DESCRIPTION OF THE INVENTION

The most basic form of the invention is shown in the coextrudedstructure of FIG. 1, which is generally designated 10. The structure hasthree layers which are, respectively, a polypropylene layer 12, anadhesive blend layer of a maleic anhydride graft copolymer ofpolypropylene and an ungrafted polypropylene 14, and a nylon layer 16.

Layer 12 may be a polypropylene homopolymer, a propylene ethylenecopolymer, or a blend of polypropylene and polyethylene. In any event,the maximum acceptable ethylene content is about 20% by weight of thelayer 12 composition. The polymer resin, or blends of resin, must, ofcourse, be extrudable polymers. A preferred polymer for layer 12 is soldunder the tradename of Hercules SA-752, which also contains about 4%ethylene. Another suitable polymer is Eastman 4G7DP, which containssmall amounts of ethylene vinyl acetate.

Layer 16 is a polymer, copolymer, or blend thereof selected from thenylon family of polyamides. Very desirable polymeric compositions forlayer 16 are nylon 6, nylon 6,6, nylon 6, 6, 6, blends of nylon 6 withless than 25% nylon 12, blends of at least about 75% nylon 6 with anyother polymer composition processable with nylon 6. Examples ofmaterials which can be processed with nylon 6 as a blend are highdensity polyethylene, medium density polyethylene, low densitypolyethylene and polypropylene. In general, any extrudable polymer maybe satisfactorily used so long as it neither degrades at the processingtemperature of about 500° F. to about 530° F., nor reacts appreciablywith the nylon 6.

Less desirable, but acceptable, are copolymers of nylon 6 and nylon 12.Unacceptable for layer 16 is nylon 12.

Processing additives such as slip agents and the like may besatisfactorily used.

Layer 14 serves as a coextruded adhesive layer between layers 12 and 16.It forms an inseparable bond with layer 12, and has good adhesion tolayer 16. Layer 14 is a blend of two components: (1) a grafted copolymerof polypropylene and maleic anhydride and (2) an ungraftedpolypropylene. The ungrafted polypropylene component (2) may be apolypropylene homopolymer, a propylene ethylene copolymer, or a blend ofpolypropylene and polyethylene. In any event, the maximum acceptableethylene content is about 20% by weight of the ungrafted polypropylenecomponent (2) of the blend.

The grafted copolymer component (1) of the blend is a copolymer producedin a reaction carried out at a temperature of from about 80° C. up toabout 10° C. below the melting point of the polypropylene, as taught inU.S. Pat. No. 3,414,551. In the reaction, crystalline polypropylene inparticulate form is agitated in contact with maleic anhydride and anorganic peroxygen compound in an atmosphere of inert gas and in theabsence of a solvent. At the conclusion of the reaction the product iswashed with water or other liquid. For use in this invention, the graftcopolymer component of the blend should contain from 0.1% to 2.5% maleicanhydride based on the total weight of the graft copolymer. A graftcopolymer suitable for use in this invention as component (1) of theblend is sold by Hercules Chemical Company as Hercoprime A-35.

The blend for coextrusion as layer 14 in the coextended structure isfrom about 5% to about 30% by weight of the maleic anhydride graftedcopolymer, and preferably about 5% to about 10%, and from about 70% toabout 95% of the ungrafted polypropylene, preferably about 90% to about95%. Thus the overall maleic anhydride concentration in the blend layer14, based on the entire blend composition, is from about 0.005% to about0.75%, with a preferred maleic anhydride concentration range of about0.005% to about 0.25%.

In the preferred extrusion process the components of the individuallayers are fed into the infeed hoppers of extruders of like number, eachextruder handling the material for one of the layers. As in the case ofthe five layer structure, illustrated, where two layers are identical,one extruder may handle the two identical layers. The melted andplasticated streams from the individual extruders are fed into amultiple manifold coextrusion die. The layers are juxtaposed andcombined in the die, and exit the die as a single multiple layer film ofpolymeric material.

After exiting the die, the polymeric material is cast onto a firstcontrolled temperature roll, passes around the first roll, and thenceonto a second controlled temperature roll, which is normally cooler thanthe first roll. The controlled temperature rolls largely control therate of cooling of the film after it exits the die. Typical operatingtemperatures for the first and second controlled temperature rolls are160° F. and 120° F. respectively.

In another embodiment of the invention illustrated in FIG. 2, afive-layer structure is coextruded, wherein similar 100 series numbersrepresent similar layers in FIG. 1. Thus the entire structure isgenerally designated 110. Layers 112, 114, and 116 have the samecompositions, and serve the same functions as layers 12, 14, and 16respectively in FIG. 1. Layer 118 is a high gas barrier material such asEVOH. Layer 120 is a layer of nylon, and may be any nylon which may becoextruded with the gas barrier material.

EXAMPLE 1

Five parts by weight of Hercoprime A-35 particles were blended with 95parts by weight of pelletized Hercules SA-752 ungrafted polypropylenepolymer to form the adhesive blend composition. A three layer film wascast coextruded through a 3-manifold cast die fed by three extrudersprocessing, respectively, nylon 6, the above recited blend, and HerculesSA-752 polypropylene. Die temperature was 500° F. Line speed was 60 feetper minute. The film was cast onto a first controlled temperature chillroll maintained at 160° F., and passed from there onto a second chillroll at 120° F. The final film was 4.5 mils thick. The outer layers were3.5 mils SA-752 polypropylene and 0.5 mil nylon, with a 0.5 mil layer ofthe blend serving as the adhesive layer between them.

EXAMPLE 2

A three layer 4.5 mil film was cast coextruded as in EXAMPLE 1, using asthe nylon layer a blend of 75% Nylon 6 and 25% Nylon 12.

EXAMPLE 3

A three layer, 4.5 mil, film was cast coextruded as in EXAMPLE 1, usingas the adhesive blend a composition of 10 parts by weight HercoprimeA-35 and 90 parts by weight SA-752.

EXAMPLE 4

A three layer, 4.5 mil, film was cast coextruded as in EXAMPLE 2, usingas the adhesive blend a composition of 10 parts by weight HercoprimeA-35 and 90 parts by weight SA-752.

EXAMPLE 5

Five parts by weight of Hercoprime A-35 particles were blended with 95parts by weight of pelletized Hercules SA-752 polypropylene to form theadhesive blend composition. Using four extruders, a 3-manifold cast die,and a combining head, a five layer film was cast coextruded. Oneextruder fed as SA-752 polypropylene stream into the die. Anotherextruder fed a stream of the adhesive blend into the die. The thirdstream was generated by two extruders feeding the nylon and EVOH intothe combining head. In the combining head, the extrudates from the twoextruders were combined into a three-layer stream having nylon on itsouter portions and a core layer of EVOH. Combining head temperature was500° F. The three-layer stream was fed from the combining adaptor intothe 3-manifold die, where it was juxtaposed, and finally, joined withthe adhesive blend layer. Die temperature was 500° F. The finalfive-layer film was cast onto a first controlled temperature chill rollmaintained at 160° F., and passed from there onto a second chill roll at120° F. Line speed was 60 feet per minute. The final film was 5 milsthick and had the following distinct layers, in order:

    ______________________________________                                        polypropylene        3.5    mils                                              adhesive blend       0.5    mil                                               Nylon 6              0.25   mil                                               EVOH                 0.5    mil                                               Nylon 6              0.25   mil                                               ______________________________________                                    

EXAMPLE 6

A five-layer, 5 mil, film was cast coextruded as in EXAMPLE 5, using, asthe nylon layers, a blend of 75% Nylon 6 and 25% Nylon 12.

EXAMPLE 7

A five-layer, 5 mil, film was cast coextruded as in EXAMPLE 5, using asthe adhesive blend a composition of 10 parts by weight Hercomprime A-35and 90 parts by weight SA-752.

EXAMPLE 8

A five-layer, 5 mil, film was cast coextruded as in EXAMPLE 6, using asthe adhesive blend a composition of 10 parts by weight Hercoprime A-35and 90 parts by weight SA-752.

The adhesive bond between layers 14 and 16 was measured as peel strengthin pounds per one inch width strip of specimen. In preparation for thepeel test, specimens were cut into one inch strips. They were thentested in a Chatillon tester, manufactured by John Chatillon and Sons,New York. Crossing head speed was 10 inches per minute. The resultingpeel strengths of all the samples were 2 lbs./in. width, with a range of1.8 to 2.1 lb./in. width.

What is claimed is:
 1. A process for producing a multiple layer plasticfilm comprising coextruding a multiple layer film from a multiple layerdie, said film comprising:(a) a layer of polypropylene; (b) a layer ofnylon; and (c) an adhesive layer juxtaposed between said nylon layer andsaid polypropylene layer, said adhesive layer being functional foradhesion to said layer of nylon and said layer of polypropylene, saidadhesive layer being a blend of a graft copolymer of maleic anhydrideonto a polypropylene backbone, and an ungrafted polypropylene; saidgraft copolymer having been produced in a reaction carried out at atemperature of from about 80° Celsius up to about 10° Celsius below themelting point of the polypropylene, said graft copolymer containing fromabout 0.1% to 2.5% maleic anhydride based on the total weight of thegraft copolymer, said graft copolymer comprising between about 5% and30% by weight of the blend, and said ungrafted polypropylene comprisingbetween about 70% and 95% by weight of the blend.
 2. A process as inclaim 1 wherein the polypropylene layer in subparagraph (a) contains upto about 20% polymeric ethylene.
 3. A process as in claim 1, said graftcopolymer reaction having taken place in the presence of an organicperoxide.
 4. A process as in claim 2, said graft copolymer reactionhaving taken place in the presence of an organic peroxide.
 5. A processfor producing a multiple layer plastic film comprising coextruding amultiple layer film from a multiple layer die, said film comprising:(a)a layer of polypropylene; (b) a layer of nylon; and (c) an adhesivelayer juxtaposed between said nylon layer and said polypropylene layer,said adhesive layer being functional for adhesion to said layer of nylonand said layer of polypropylene, said adhesive layer being a blend of agraft copolymer of maleic anhydride onto a polypropylene backbone, andan ungrafted polypropylene; said graft copolymer containing from about0.1% to 2.5% maleic anhydride based on the total weight of the graftcopolymer, said graft copolymer comprising between about 5% and 30% byweight of the blend, and said ungrafted polypropylene comprising betweenabout 70% and 95% by weight of the blend.
 6. A process as in claim 5,wherein the polypropylene layer in subparagraph (a) contains up to about20% polymeric ethylene.
 7. A process as in claim 5, said graft copolymerreaction having taken place in the presence of an organic peroxide.
 8. Aprocess as in claim 6, said graft copolymer reaction having taken placein the presence of an organic peroxide.
 9. A process for producing amultiple layer plastic film comprising coextruding a multiple layer filmfrom a multiple layer die, said film comprising:(a) a layer ofpolypropylene; (b) a layer of nylon; and (c) an adhesive layerjuxtaposed between said nylon layer and said polypropylene layer, saidadhesive layer being functional for adhesion to said layer of nylon andsaid layer of polypropylene, said adhesive layer being a blend of agraft copolymer of maleic anhydride onto an olefin polymer or copolymer,and an ungrafted polypropylene; said grafted copolymer containing fromabout 0.1% to 2.5% maleic anhydride based on the total weight of thegrafted copolymer, said grafted copolymer comprising between about 5%and 30% by weight of the blend, and said ungrafted polypropylenecomprising between about 70% and 95% by weight of the blend.